The natural polycrystalline diamonds from the Mengyin kimberlite pipes can be classified as the euhedral faceted polycrystalline diamonds and anhedral rounded polycrystalline diamonds. The results of micro-FTIR spectra characterization of the polycrystalline diamonds show that the concentration of nitrogen is low, varying from 16.69 to 72.81 microgram per gram and is different among different diamond grains or position in polycrystalline diamonds. The euhedral faceted polycrystalline diamonds are ⅠaAB type and have higher concentration of A-center defects than B-center defects. Most of the anhedral rounded polycrystalline diamonds are ⅠaAB type and have higher content of B-center defects. A minority of the anhedral rounded polycrystalline diamonds have C-center, A-center and B-center defects simultaneously. The polycrystalline diamonds probably originated from the relatively deeper mantle and were not formed in diamond nucleation stage, but in the diamond growth period or some special conditions after the diamond grains were formed already. Furthermore, the euhedral faceted polycrystalline diamonds were formed slightly later and the anhedral rounded polycrystalline diamonds were formed obviously earlier than the diamond single crystals from the Mengyin kimberlite pipes.